US4992585A - Process for producing α-chloroacetoacetic acid monomethylamide - Google Patents
Process for producing α-chloroacetoacetic acid monomethylamide Download PDFInfo
- Publication number
- US4992585A US4992585A US07/421,572 US42157289A US4992585A US 4992585 A US4992585 A US 4992585A US 42157289 A US42157289 A US 42157289A US 4992585 A US4992585 A US 4992585A
- Authority
- US
- United States
- Prior art keywords
- mother liquor
- weight
- acid monomethylamide
- monomethylamide
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- XIWMZCRVSYHMER-UHFFFAOYSA-N 2-chloro-n-methyl-3-oxobutanamide Chemical compound CNC(=O)C(Cl)C(C)=O XIWMZCRVSYHMER-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 28
- 239000012452 mother liquor Substances 0.000 claims abstract description 52
- ATWLCPHWYPSRBQ-UHFFFAOYSA-N N-Methylacetoacetamide Chemical compound CNC(=O)CC(C)=O ATWLCPHWYPSRBQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- -1 alkali metal salts Chemical class 0.000 claims abstract description 3
- 239000012442 inert solvent Substances 0.000 claims abstract description 3
- 238000000605 extraction Methods 0.000 claims description 24
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 238000004064 recycling Methods 0.000 claims description 8
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- VCBFAUSKNYAKJZ-UHFFFAOYSA-N 2-chloro-3-oxobutanoic acid Chemical compound CC(=O)C(Cl)C(O)=O VCBFAUSKNYAKJZ-UHFFFAOYSA-N 0.000 claims 1
- HOZLOOPIXHWKCI-UHFFFAOYSA-N 2-chloro-n-methylacetamide Chemical compound CNC(=O)CCl HOZLOOPIXHWKCI-UHFFFAOYSA-N 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 239000000047 product Substances 0.000 description 11
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- BLQDAFLFPNDCMJ-UHFFFAOYSA-N 2,2-dichloro-n-methylacetamide Chemical compound CNC(=O)C(Cl)Cl BLQDAFLFPNDCMJ-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 3
- AOOLFYMBFIGYDE-UHFFFAOYSA-N 2-chloro-3-oxobutanamide Chemical class CC(=O)C(Cl)C(N)=O AOOLFYMBFIGYDE-UHFFFAOYSA-N 0.000 description 2
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical class CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 description 2
- 239000012431 aqueous reaction media Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- KRTSDMXIXPKRQR-AATRIKPKSA-N monocrotophos Chemical compound CNC(=O)\C=C(/C)OP(=O)(OC)OC KRTSDMXIXPKRQR-AATRIKPKSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/72—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms
- C07C235/80—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms having carbon atoms of carboxamide groups and keto groups bound to the same carbon atom, e.g. acetoacetamides
Definitions
- the present invention relates to a process for producing ⁇ -chloroacetoacetic acid monomethylamide by chlorination of acetoacetic acid monomethylamide in an aqueous medium.
- ⁇ -Chloroacetoacetic acid monomethylamide is a valuable intermediate for producing insecticidal active substances. It produces for example, on reaction with trimethyl-phosphite, O,O-dimethyl-O-(1-methyl-2-methylcarbamoylvinyl) phosphate, which has become known, under the name of monocrotophos, as an active ingredient in insecticidal compositions.
- the product obtained is 95.5-97.4% pure and contains 2.0-2.5% by weight of unreacted starting material and 0.6-1.5% by weight of ⁇ , ⁇ -dichlorinated product. While this process is satisfactory with respect to yield and purity of the product it is complicated and uneconomical in view of the large amount of organic solvent used in the extraction and its removal from the extract by distillation.
- a method of producing ⁇ -chloroacetoacetic acid monomethylamide by reaction of chlorine with acetoacetic acid monomethylamide in an aqueous medium, at temperatures of -20°to +10° C., in the presence of urea and alkali metal salts, neutralisation of the reaction mixture, separation of solid ⁇ -chloroacetoacetic acid monomethylamide, and feeding back of the mother liquor into the chlorination reaction, the procedure being such that the mother liquor obtained each time after the separation of ⁇ -chloroacetoacetic acid monomethylamide is extracted, before being recycled, with 2-10% by weight of an inert solvent immiscible with water, relative to the total amount of mother liquor.
- Suitable solvents for the extraction of the mother liquor are aliphatic and aromatic hydrocarbons, such as hexane, heptane, cyclohexane, benzene toluene and xylene; also halogenated aliphatic and aromatic hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene.
- Particularly favourable solvents are 1,2-dichloroethane and toluene.
- the extraction can be carried out either batchwise, in a single stage or in several steps, in a vessel with stirrers, or continuously in extraction columns having 1-10 preferably 3-5, theoretical separation stages. In the case of the continuous procedure, it is possible to separate according to both the co-current and the counter-current principle. On a account of the corrosive properties of the mother liquor, it is advantageous to use apparatus made from glass, enamel or high-alloy steels, for example Hastelloy C.
- For the single-stage extraction in a vessel with stirrer there is preferably used 4-6% by weight of solvent, and for the multistage extraction preferably 3-5% by weight, relative to the total amount of mother liquor to be extracted. Extraction can be performed in the temperature range of -20° to 50° C., and takes 15 minutes to 2 hours. The extraction is preferably carried out at 0°-20° C.
- the solvent used for extraction can be recovered from the extract by distillation and can be re-used.
- the distillation residue contains, besides ⁇ , ⁇ -dichloroacetoacetic acid monomethylamide and acetoacetic acid monomethylamide, also ⁇ -chloroacetoacetic acid monomethylamide. These substances can be recovered from the distillation residue by fractional crystallisation from toluene or 1,2-dichloroethane.
- the ⁇ -chloroacetoacetic acid monomethylamide contained in the distillation residue is obtained in this manner to the extent of 50-70%.
- the extraction of the mother liquor in the manner according to the invention enables, in contrast to the known process, the recyclisation of the whole of the mother liquor.
- the losses occurring in the production of ⁇ -chloroacetoacetic acid monomethylamide can thus be reduced to a minimum.
- the ⁇ -chloroacetoacetic acid monomethylamide is obtained with a higher level of purity and in better yield compared with the corresponding results obtainable with the known process.
- the composition of the extracted mother liquor remains unchanged and a practically infinite number of recyclisation can be carried out with the total amount of extracted mother liquor. Due to the lower contents of impurities of the extracted mother liquor as compared with the unextracted mother liquor of the old process the yield of ⁇ -chloroacetoacetic acid monomethylamide obtained in each batch is increased to about 75% of theory calculated on the amount of freshly added acetoacetic acid monomethylamide while, at the same time, the purity of the product is increased to about 91%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH263684 | 1984-05-29 | ||
| CH2636/84-0 | 1984-05-29 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07350991 Continuation-In-Part | 1989-05-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4992585A true US4992585A (en) | 1991-02-12 |
Family
ID=4238215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/421,572 Expired - Fee Related US4992585A (en) | 1984-05-29 | 1989-10-16 | Process for producing α-chloroacetoacetic acid monomethylamide |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4992585A (enrdf_load_stackoverflow) |
| EP (1) | EP0166685B1 (enrdf_load_stackoverflow) |
| JP (1) | JPS6148A (enrdf_load_stackoverflow) |
| KR (1) | KR930006194B1 (enrdf_load_stackoverflow) |
| AT (1) | ATE39478T1 (enrdf_load_stackoverflow) |
| DE (1) | DE3567015D1 (enrdf_load_stackoverflow) |
| IL (1) | IL75328A (enrdf_load_stackoverflow) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2145602C1 (ru) * | 1994-12-30 | 2000-02-20 | Де Вэллкам Фаундейшн Лимитед | Способы получения ламотриджина, промежуточные соединения и способ получения фармацевтической композиции |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740702A (en) * | 1986-01-22 | 1988-04-26 | Nicolet Instrument Corporation | Cryogenically cooled radiation detection apparatus |
| KR100399221B1 (ko) * | 1998-12-26 | 2003-12-24 | 주식회사 포스코 | 고자속밀도일방향성전기강판의제조방법 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3483252A (en) * | 1966-02-21 | 1969-12-09 | Ciba Ltd | Partial chlorination of acetoacetic acid monoalkylamides |
| US3917694A (en) * | 1974-04-12 | 1975-11-04 | Shell Oil Co | Chlorination of 3-oxoalkanamides |
| US4207259A (en) * | 1978-06-01 | 1980-06-10 | Wacker-Chemie Gmbh | Process for the manufacture of α-chloracetoacetamides |
| US4235818A (en) * | 1977-06-30 | 1980-11-25 | Ciba-Geigy Corporation | Process for producing alpha-monochloroacetoacetic acid monomethylamide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH634547A5 (de) * | 1977-06-30 | 1983-02-15 | Ciba Geigy Ag | Verfahren zur herstellung von alpha-monochloracetessigsaeuremonomethylamid. |
-
1985
- 1985-05-23 AT AT85810243T patent/ATE39478T1/de active
- 1985-05-23 EP EP85810243A patent/EP0166685B1/de not_active Expired
- 1985-05-23 DE DE8585810243T patent/DE3567015D1/de not_active Expired
- 1985-05-28 IL IL75328A patent/IL75328A/xx not_active IP Right Cessation
- 1985-05-28 KR KR1019850003650A patent/KR930006194B1/ko not_active Expired - Fee Related
- 1985-05-29 JP JP60116320A patent/JPS6148A/ja active Granted
-
1989
- 1989-10-16 US US07/421,572 patent/US4992585A/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3483252A (en) * | 1966-02-21 | 1969-12-09 | Ciba Ltd | Partial chlorination of acetoacetic acid monoalkylamides |
| US3917694A (en) * | 1974-04-12 | 1975-11-04 | Shell Oil Co | Chlorination of 3-oxoalkanamides |
| US4235818A (en) * | 1977-06-30 | 1980-11-25 | Ciba-Geigy Corporation | Process for producing alpha-monochloroacetoacetic acid monomethylamide |
| US4207259A (en) * | 1978-06-01 | 1980-06-10 | Wacker-Chemie Gmbh | Process for the manufacture of α-chloracetoacetamides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2145602C1 (ru) * | 1994-12-30 | 2000-02-20 | Де Вэллкам Фаундейшн Лимитед | Способы получения ламотриджина, промежуточные соединения и способ получения фармацевтической композиции |
Also Published As
| Publication number | Publication date |
|---|---|
| IL75328A0 (en) | 1985-09-29 |
| JPS6148A (ja) | 1986-01-06 |
| DE3567015D1 (en) | 1989-02-02 |
| KR850008334A (ko) | 1985-12-16 |
| KR930006194B1 (ko) | 1993-07-08 |
| ATE39478T1 (de) | 1989-01-15 |
| EP0166685B1 (de) | 1988-12-28 |
| IL75328A (en) | 1988-11-15 |
| EP0166685A1 (de) | 1986-01-02 |
| JPH0437072B2 (enrdf_load_stackoverflow) | 1992-06-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: CIBA-GEIGY CORPORATION, 444 SAW MILL RIVER ROAD, A Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:RIGAMONTI, FLAVIANO;RAGHUNANDAN, PULLISSERY;REEL/FRAME:005535/0681;SIGNING DATES FROM 19890914 TO 19890926 |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19990212 |
|
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |